CN113166520A

CN113166520A - Thermoplastic resin composition and molded article comprising the same

Info

Publication number: CN113166520A
Application number: CN202080006748.6A
Authority: CN
Inventors: 成多恩; 金泰勋; 朴春浩; 安勇希; 赵旺来; 金豪焄; 张正敃
Original assignee: LG Chem Ltd
Current assignee: LG Chem Ltd
Priority date: 2019-09-06
Filing date: 2020-08-25
Publication date: 2021-07-23
Anticipated expiration: 2040-08-25
Also published as: US20220010122A1; EP3872132A4; KR20210029670A; TW202116907A; EP3872132A1; CN113166520B; JP2022514577A; KR102465681B1; US11884810B2

Abstract

The present invention relates to a thermoplastic resin composition and a molded article comprising the same. More specifically, the thermoplastic resin composition of the present invention comprises: 100 parts by weight of a base resin consisting of 10 to 30% by weight of an acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (a-1) containing an acrylate rubber having an average particle diameter of 0.05 to 0.15 μm, 20 to 40% by weight of an acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (a-2) containing an acrylate rubber having an average particle diameter of 0.3 to 0.5 μm, 0 to 35% by weight of an aromatic vinyl polymer (B), and 10 to 60% by weight of a polymethacrylate (C); and 0.5 to 10 parts by weight of a polyamide (D). According to the present invention, it is possible to provide a low-gloss thermoplastic resin composition having mechanical properties and processability equal to or better than those of conventional ASA-based resins, having excellent weather resistance, exhibiting good aesthetic properties and soft feeling due to its low surface roughness value, and having uniform surface gloss, and to provide a molded article comprising the same.

Description

Thermoplastic resin composition and molded article comprising the same

Technical Field

[ Cross-reference to related applications ]

The present application claims the priority of korean patent application No.10-2019-0110417 filed by the korean intellectual property office at 6.9.2019 and korean patent application No.10-2020-0106135 filed by the korean intellectual property office at 24.8.2020 based on the priority of the above patents, the disclosures of each of which are incorporated herein by reference.

The present invention relates to a thermoplastic resin composition and a molded article comprising the same, and more particularly, to a thermoplastic resin composition having mechanical properties and processability equal to or better than those of conventional ASA-based resins; has excellent weather resistance; exhibit good aesthetics (aesthtics) and soft feel due to its low surface roughness value; and a low-gloss thermoplastic resin composition having uniform surface gloss, and a molded article comprising the same.

Background

An acrylate compound-styrene-acrylonitrile copolymer (hereinafter, referred to as "ASA resin") has good weather resistance, aging resistance, chemical resistance, rigidity, impact resistance and processability, and is widely used in various fields such as automobiles, sundry goods and building materials due to its wide applicability.

However, in the field of exterior materials, there is an increasing demand for development of low-gloss ASA resins that satisfy consumer aesthetic requirements in addition to the artificial feel of plastics.

As an example of the low gloss ASA resin, a crystalline resin such as nylon has been developed. When the crystalline resin is used, low gloss can be achieved, but there is a limitation in improving physical properties of exterior materials such as weather resistance and surface texture.

[ related art documents ]

[ patent document ] (patent document 1) KR 2009-0095764A

Disclosure of Invention

Technical problem

Accordingly, the present invention has been made in view of the above problems, and it is an object of the present invention to provide a resin composition having mechanical properties and processability equal to or better than those of conventional ASA-based resins; has excellent weather resistance; exhibits good aesthetics and soft feel due to its low surface roughness value; and a low-gloss thermoplastic resin composition having uniform surface gloss, and a molded article comprising the same.

The above and other objects can be accomplished by the present disclosure described below.

Technical scheme

According to an aspect of the present invention, there is provided a thermoplastic resin composition comprising: 100 parts by weight of a base resin consisting of 10 to 30% by weight of an acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (a-1) containing an acrylate rubber having an average particle diameter of 0.05 to 0.15 μm, 20 to 40% by weight of an acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (a-2) containing an acrylate rubber having an average particle diameter of 0.3 to 0.5 μm, 0 to 35% by weight of an aromatic vinyl polymer (B), and 10 to 60% by weight of a polymethacrylate (C); and 0.5 to 10 parts by weight of a polyamide (D), and a molded article comprising the thermoplastic resin composition.

Advantageous effects

As is apparent from the foregoing, the present invention advantageously provides a resin composition having mechanical properties and processability equal to or better than those of conventional ASA-based resins; has excellent weather resistance; exhibits good aesthetics and soft feel due to its low surface roughness value; and a low-gloss thermoplastic resin composition having uniform surface gloss, and a molded article comprising the same.

Detailed Description

Hereinafter, the thermoplastic resin composition of the present invention and a molded article comprising the same will be described in detail.

The present inventors confirmed that, in order to obtain a matte effect by adding polyamide to an ASA resin, when the morphology of the ASA resin is adjusted and a methyl methacrylate-styrene-acrylonitrile copolymer or polymethyl methacrylate is contained as a main component in a predetermined composition ratio, a resin having mechanical properties and processability equal to or better than those of conventional ASA-based resins is obtained; has excellent weather resistance; exhibits good aesthetics and soft feel due to its low surface roughness value; and a low-gloss thermoplastic resin composition having uniform surface gloss. Based on these results, the present inventors have further conducted studies to complete the present invention.

The thermoplastic resin composition of the present invention comprises: 100 parts by weight of a base resin consisting of 10 to 30% by weight of an acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (a-1) containing an acrylate rubber having an average particle diameter of 0.05 to 0.15 μm, 20 to 40% by weight of an acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (a-2) containing an acrylate rubber having an average particle diameter of 0.3 to 0.5 μm, 0 to 35% by weight of an aromatic vinyl polymer (B), and 10 to 60% by weight of a polymethacrylate (C); and 0.5 to 10 parts by weight of a polyamide (D). In this case, it is possible to provide a resin composition having mechanical properties and processability equal to or better than those of conventional ASA-based resins; has excellent weather resistance; low gloss and uniform surface gloss; and exhibits good aesthetic properties and soft feel due to its low surface roughness value.

Hereinafter, the respective components constituting the thermoplastic resin composition of the present invention will be described in detail.

A-1) acrylate-aromatic vinyl Compound-vinyl cyanide Compound graft copolymer

For example, the graft copolymer (A-1) may contain an acrylate rubber having an average particle diameter of 0.05 μm to 0.15. mu.m, preferably 0.1 μm to 0.15. mu.m, more preferably 0.12 μm to 0.15. mu.m, still more preferably 0.12 μm to 0.14 μm or 0.13 μm to 0.15. mu.m. Within this range, the finally prepared thermoplastic resin composition may have excellent weather resistance, colorability, impact strength, chemical resistance and surface gloss.

The acrylate rubber is preferably a core.

In the present specification, the average particle diameter can be measured by dynamic light scattering, specifically using Nicomp 380 (manufacturer: PSS).

In addition, in the present specification, the average particle diameter may refer to an arithmetic average particle diameter in a particle diameter distribution measured by dynamic light scattering, specifically, an average particle diameter of scattering intensity.

For example, the content of the graft copolymer (A-1) may be 10 to 30% by weight, preferably 15 to 25% by weight, more preferably 15 to 20% by weight. Within this range, weather resistance, flowability, tensile strength, and impact strength may be excellent.

For example, the graft copolymer (a-1) may include 40 to 60% by weight of the acrylate rubber, 25 to 45% by weight of the aromatic vinyl compound, and 10 to 20% by weight of the vinyl cyanide compound. Within this range, weather resistance, flowability, tensile strength, and impact strength may be excellent.

As a preferred example, the graft copolymer (a-1) may include 45 to 55% by weight of the acrylate rubber, 30 to 50% by weight of the aromatic vinyl compound, and 5 to 20% by weight of the vinyl cyanide compound. Within this range, weather resistance, flowability, tensile strength, and impact strength may be excellent.

As a more preferred example, the graft copolymer (a-1) may include 45 to 55% by weight of the acrylate rubber, 30 to 40% by weight of the aromatic vinyl compound, and 10 to 20% by weight of the vinyl cyanide compound. Within this range, weather resistance, flowability, tensile strength, and impact strength may be excellent.

In the present specification, a polymer including a specific compound refers to a polymer prepared by polymerizing the compound, and a unit in the polymer is derived from the compound.

For example, the graft copolymer (A-1) can be prepared by emulsion polymerization. In this case, chemical resistance, weather resistance, fluidity, tensile strength, and impact strength may be excellent.

The emulsion graft polymerization method generally practiced in the art to which the present invention pertains may be used as the emulsion polymerization method of the present invention without particular limitation.

For example, the acrylate may include one or more selected from alkyl acrylates including an alkyl group having 2 to 8 carbon atoms. Preferably, the acrylate comprises an alkyl acrylate comprising an alkyl group having 4 to 8 carbon atoms, more preferably butyl acrylate or ethylhexyl acrylate.

For example, the aromatic vinyl compound may include one or more selected from styrene, α -methylstyrene, m-methylstyrene, p-methylstyrene and p-tert-butylstyrene, preferably styrene.

For example, the vinyl cyanide compound may include one or more selected from acrylonitrile, methacrylonitrile, ethacrylonitrile, and isopropylacrylonitrile, preferably acrylonitrile.

A-2) acrylate-aromatic vinyl Compound-vinyl cyanide Compound graft copolymer

For example, the graft copolymer (A-2) may include an acrylate rubber having an average particle diameter of 0.3 μm to 0.5. mu.m, preferably 0.35 μm to 0.5. mu.m, more preferably 0.4 μm to 0.5. mu.m, still more preferably 0.45 μm to 0.50. mu.m. Within this range, the weather resistance may be good, and the fluidity and mechanical strength, such as tensile strength and impact strength, may be excellent.

The acrylate rubber is preferably a core.

For example, the content of the graft copolymer (A-2) may be 20 to 40% by weight, preferably 25 to 35% by weight, more preferably 30 to 35% by weight. Within this range, weather resistance, flowability, tensile strength, and impact strength may be excellent.

For example, the graft copolymer (a-2) may include 40 to 60% by weight of the acrylate rubber, 25 to 45% by weight of the aromatic vinyl compound, and 10 to 20% by weight of the vinyl cyanide compound. Within this range, weather resistance, flowability, tensile strength, and impact strength may be excellent.

As a preferred example, the graft copolymer (a-2) may include 45 to 55% by weight of the acrylate rubber, 30 to 40% by weight of the aromatic vinyl compound, and 10 to 20% by weight of the vinyl cyanide compound. Within this range, weather resistance, flowability, tensile strength, and impact strength may be excellent.

The graft copolymer (A-1) is preferably contained in a smaller amount than the graft copolymer (A-2). More preferably, the weight ratio between the graft copolymer (A-1) and the graft copolymer (A-2) is from 1:1.1 to 1:4, still more preferably from 1:1.2 to 1: 2. Within this range, weather resistance, flowability, tensile strength, and impact strength may be excellent.

The total weight of the graft copolymer (A-1) and the graft copolymer (A-2) is preferably 40 to 60% by weight, more preferably 45 to 55% by weight, still more preferably 47 to 53% by weight, based on the weight of the base resin. Within this range, weather resistance, flowability, tensile strength, and impact strength may be excellent.

For example, the graft copolymer (A-2) can be prepared by emulsion polymerization. In this case, weather resistance, fluidity, tensile strength, and impact strength may be excellent.

B) Aromatic vinyl polymer

For example, the content of the aromatic vinyl polymer (B) may be 0 to 35% by weight, preferably 10 to 35% by weight, more preferably less than 10% by weight, and still more preferably less than 5% by weight. Most preferably, the aromatic vinyl polymer (B) is absent. Within this range, the weather resistance may be excellent, and the surface roughness value may be significantly reduced, thereby achieving uniform glossiness and soft touch.

The aromatic vinyl polymer (B) preferably contains 65 to 80% by weight of an aromatic vinyl compound and 20 to 35% by weight of a vinyl cyanide compound. Within this range, chemical resistance and impact strength may be excellent.

For example, the weight average molecular weight of the aromatic vinyl polymer (B) may be 80,000g/mol to 180,000g/mol, preferably 80,000g/mol to 160,000 g/mol. Within this range, the tensile strength and impact strength may be excellent.

For example, the aromatic vinyl polymer (B) may be an aromatic vinyl compound-vinyl cyan compound copolymer. As a preferred example, the aromatic vinyl polymer (B) may be a styrene-acrylonitrile copolymer (SAN resin), an α -methylstyrene-acrylonitrile copolymer (heat-resistant SAN resin), or a mixture thereof. In this case, the heat resistance may be excellent.

The content of the styrene-acrylonitrile copolymer is preferably 15 to 35% by weight, more preferably 15 to 25% by weight. Within this range, the heat resistance may be excellent.

The styrene-acrylonitrile copolymer preferably contains 65 to 80% by weight of styrene and 20 to 35% by weight of acrylonitrile. Within this range, processability and impact strength may be excellent.

For example, the weight average molecular weight of the styrene-acrylonitrile copolymer may be 100,000g/mol to 180,000g/mol, preferably 100,000g/mol to 150,000 g/mol. Within this range, the heat resistance may be excellent.

The content of the α -methylstyrene-acrylonitrile copolymer is preferably 10 to 20% by weight, more preferably 12 to 18% by weight. Within this range, the heat resistance may be excellent.

The alpha-methylstyrene-acrylonitrile copolymer preferably comprises 70 to 75% by weight of alpha-methylstyrene and 25 to 30% by weight of acrylonitrile, more preferably 60 to 75% by weight of alpha-methylstyrene, 0 to 10% by weight of styrene, and 20 to 30% by weight of acrylonitrile or 60 to 70% by weight of alpha-methylstyrene, 0 to 10% by weight of styrene, and 25 to 30 wt% acrylonitrile, still more preferably 60 to 75 wt% alpha-methylstyrene, 5 to 10 wt% styrene and 20 to 30 wt% acrylonitrile or 60 to 70 wt% alpha-methylstyrene, 5 to 10 wt% styrene, and 25 to 30 wt% acrylonitrile. Within this range, the heat resistance may be excellent.

The weight average molecular weight of the α -methylstyrene-acrylonitrile copolymer is preferably from 80,000g/mol to 120,000 g/mol. Within this range, the heat resistance may be excellent.

In the present specification, unless otherwise defined, the weight average molecular weight can be measured using gel permeation chromatography (GPC, Waters Breeze). As a specific example, the weight average molecular weight can be measured by gel permeation chromatography (GPC, Waters Breeze) using Tetrahydrofuran (THF) as an eluent. In this case, the weight average molecular weight was obtained as a relative value to a standard Polystyrene (PS) sample.

For example, the aromatic vinyl polymer (B) may be prepared using suspension polymerization, emulsion polymerization, solution polymerization, or bulk polymerization. In this case, heat resistance and fluidity may be excellent.

Suspension polymerization, emulsion polymerization, solution polymerization and bulk polymerization, which are generally carried out in the art to which the present invention pertains, may be used in the present invention without particular limitation.

C) Polymethacrylate

For example, the content of the polymethacrylate (C) may be 10 to 60% by weight, preferably 25 to 55% by weight, more preferably 25 to 50% by weight, still more preferably 30 to 50% by weight, still more preferably 35 to 50% by weight, and most preferably 45 to 50% by weight. Within this range, a thermoplastic resin composition having mechanical properties and processability equal to or better than those of conventional ASA-based resins and having excellent weather resistance can be prepared. In addition, the surface roughness value can be greatly reduced, thereby achieving good aesthetics and soft feel.

The polymethacrylate (C) preferably contains 55 wt% or more, preferably 60 wt% or more, and most preferably 65 wt% or more of a methacrylate monomer. Within this range, the weather resistance can be greatly improved, and the surface roughness value can be greatly reduced, thereby achieving good aesthetic properties and soft feel.

For example, the methacrylate monomer may be an alkyl methacrylate containing an alkyl group having 1 to 15 carbon atoms. As a specific example, the methacrylate monomer may include one or more selected from the group consisting of methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylbutyl methacrylate, 2-ethylhexyl methacrylate, and lauryl methacrylate, preferably an alkyl methacrylate including an alkyl group having 1 to 4 carbon atoms, and more preferably methyl methacrylate.

The polymethacrylate (C) may include one or more selected from the group consisting of a polymethylmethacrylate resin and a methylmethacrylate-styrene-acrylonitrile copolymer, preferably a polymethylmethacrylate resin or a methylmethacrylate-styrene-acrylonitrile copolymer, more preferably a polymethylmethacrylate resin. In this case, weather resistance may be excellent, and good aesthetic property and soft feeling may be achieved due to a low surface roughness value.

For example, the weight average molecular weight of the polymethyl methacrylate resin may be 35,000g/mol to 200,000g/mol, preferably 50,000g/mol to 200,000 g/mol. Within this range, weather resistance, flowability, tensile strength, and impact strength may be excellent, and good aesthetic properties and soft feel may be achieved due to a low surface roughness value.

As another example, the polymethyl methacrylate resin may be a mixture of a polymethyl methacrylate resin having a weight average molecular weight of 50,000g/mol to 200,000g/mol (hereinafter referred to as "high molecular weight PMMA resin") and a polymethyl methacrylate resin having a weight average molecular weight of 35,000g/mol to 45,000g/mol (hereinafter referred to as "low molecular weight PMMA resin").

For example, the weight ratio between the high molecular weight PMMA resin and the low molecular weight PMMA resin may be 1:0.1 to 2.0, preferably 1:1.3 to 1.7, more preferably 1:1.4 to 1.6. Within this range, fluidity, tensile strength, impact strength, and weather resistance may be excellent, and good aesthetic properties and soft feeling may be achieved due to a low surface roughness value.

In the present specification, the weight ratio between A and B means the weight ratio of A to B.

For example, the methyl methacrylate-styrene-acrylonitrile copolymer comprises 65 to 85 wt% of methyl methacrylate, 5 to 30 wt% of styrene, and 5 to 10 wt% of acrylonitrile. Within this range, weather resistance may be excellent, and good aesthetic properties and soft feel may be achieved due to a low surface roughness value.

For example, the methyl methacrylate-styrene-acrylonitrile copolymer may have a weight average molecular weight of 70,000g/mol to 140,000 g/mol. As another example, the methyl methacrylate-styrene-acrylonitrile copolymer can have a weight average molecular weight of 70,000g/mol to 90,000g/mol or greater than 90,000g/mol and less than or equal to 140,000 g/mol. Within this range, weather resistance, flowability, tensile strength, and impact strength may be excellent, and good aesthetic properties and soft feel may be achieved due to a low surface roughness value.

As another example, the methyl methacrylate-styrene-acrylonitrile copolymer may be a mixture of a methyl methacrylate-styrene-acrylonitrile copolymer having a weight average molecular weight of 70,000g/mol to 90,000g/mol (hereinafter referred to as "low molecular weight SAMMA resin") and a methyl methacrylate-styrene-acrylonitrile copolymer having a weight average molecular weight of 120,000g/mol to 140,000g/mol (hereinafter referred to as "high molecular weight SAMMA resin").

For example, the weight ratio between the low molecular weight SAMMA resin and the high molecular weight SAMMA resin may be from 1:0.1 to 0.45, preferably from 1:0.2 to 0.45, more preferably from 1:0.3 to 0.45, still more preferably from 1:0.35 to 0.45. Within this range, the weather resistance may be excellent.

For example, the polymethacrylate (C) may be prepared using solution polymerization, bulk polymerization, emulsion polymerization, or suspension polymerization. Solution polymerization, bulk polymerization, emulsion polymerization and suspension polymerization, which are generally carried out in the art to which the present invention pertains, may be used in the present invention without particular limitation.

D) Polyamide

For example, the content of the polyamide (D) may be 0.5 to 10 parts by weight, preferably 1 to 8 parts by weight, more preferably 4 to 8 parts by weight, and still more preferably 4 to 6 parts by weight, based on 100 parts by weight of the base resin. Within this range, a matte effect may be achieved due to the reduction of glossiness, and the balance of physical properties may be excellent.

The polyamide (D) means a thermoplastic polymer containing amide bonds. As specific examples, the polyamide (D) may include one or more selected from the group consisting of polyamide 6, polyamide 66(PA6.6), polyamide 46, polyamide LL, polyamide 12, polyamide 610, polyamide 612, polyamide 6/66, polyamide 6/612, polyamide MXD6, polyamide 6/MXD6, polyamide 66/MXD6, polyamide 6T, polyamide 6I, polyamide 6/6T, polyamide 6/6I, polyamide 66/6T, polyamide 66/6I, polyamide 6/6T/6I, polyamide 66/6T/6I, polyamide 9T, polyamide 9I, polyamide 6/9T, polyamide 6/9I, polyamide 66/9T, polyamide 6/12/9T, polyamide 66/12/9T, polyamide 6/12/9I and polyamide 66/12/6I, polyamide 66(PA6.6) is preferred.

For example, the polyamide (D) having a melting point of 230 ℃ or higher, preferably 240 ℃ or higher, more preferably 250 ℃ or higher, and still more preferably 260 ℃ to 270 ℃ can be used.

For example, a polyamide (D) having a relative viscosity (96% sulfuric acid solution) of 2.0 to 4.0, preferably 2.0 to 3.5, more preferably 2.0 to 3.0, and still more preferably 2.4 to 2.7 may be used.

In the present specification, the relative viscosity can be measured using an ubpellode (ubpelohde) viscometer according to ISO 307.

The polymerization method generally carried out in the field to which the present invention pertains can be used as a method for preparing the polyamide (D) without particular limitation, and a commercially available polyamide can also be used when it satisfies the definition of the polyamide of the present invention.

Thermoplastic resin composition

For example, the thermoplastic resin composition of the present invention may have an average roughness value of 5 points measured using an optical profilometer system of 4 or less, preferably 3.5 or less, more preferably 3 or less, and still more preferably 2.5 or less.

For example, the thermoplastic resin composition may have a 2,000-hour weatherability (. DELTA.E) value of 4.0 or less, preferably 3.5 or less, more preferably 3.2 or less, and still more preferably 3.0 or less, as measured according to SAE J1960.

For example, the thermoplastic resin composition may have a Melt Index (MI) (temperature: 220 ℃ C., load: 10kg) as measured according to ASTM D1238 of 3g/10min or more, preferably 7g/10min or more, more preferably 10g/10min or more, still more preferably 12g/10min or more, and as a specific example, 12g/10min to 15g/10 min.

For example, the thermoplastic resin composition may have a tensile strength (1/8 inches) of 290kg/cm as measured according to ASTM 638²Above, 380kg/cm is preferable²Above, more preferably 400kg/cm²Above, even more preferably 470kg/cm²As a specific example, the above is 380kg/cm²To 490kg/cm²。

For example, the Izod impact strength (1/4 inches) of the thermoplastic resin composition measured according to ASTM 256 may be 7 kg-cm/cm or more, preferably 9 kg-cm/cm or more, and as a specific example, 7 kg-cm/cm to 11 kg-cm/cm or 8 kg-cm/cm to 11 kg-cm/cm.

For example, the thermoplastic resin composition may have a film gloss of 14 or less, 11 or less, or 10.5 or less, preferably 9.5 or less, more preferably 9.3 or less, as a specific example, 4.8 to 14.0 or 4.8 to 11.0, measured at 60 ° using a gloss meter (product name: VG 7000). Within this range, the matte properties and physical property balance may be excellent. Therefore, the thermoplastic resin composition of the present invention may also be referred to as a matte thermoplastic resin composition.

The thermoplastic resin composition may further optionally include one or more selected from the group consisting of a heat stabilizer, a light stabilizer, a dye, a pigment, a colorant, a release agent, an antistatic agent, an antibacterial agent, a processing aid, a metal deactivator, a flame retardant, a smoke suppressant, an anti-dripping agent, an anti-friction agent and an anti-abrasion agent in an amount of 0.01 to 5 parts by weight, 0.05 to 3 parts by weight, 0.1 to 2 parts by weight or 0.5 to 1 part by weight, as required. Within this range, desired physical properties can be achieved without lowering the natural properties of the thermoplastic resin composition of the present invention.

For example, the method of preparing the thermoplastic resin composition of the present invention comprises the steps of: mixing 100 parts by weight of a base resin consisting of 10 to 30% by weight of an acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (a-1) containing an acrylate rubber having an average particle diameter of 0.05 to 0.15 μm, 20 to 40% by weight of an acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (a-2) containing an acrylate rubber having an average particle diameter of 0.3 to 0.5 μm, 0 to 35% by weight of an aromatic vinyl polymer (B), and 10 to 60% by weight of a polymethacrylate (C); and 0.5 to 10 parts by weight of a polyamide (D); and a step of preparing pellets at 220 to 280 ℃ using an extrusion mixer. In this case, it is possible to provide a resin composition having mechanical properties and processability equal to or better than those of conventional ASA-based resins; has excellent weather resistance; low gloss and uniform surface gloss; and exhibits good aesthetic properties and soft feel due to its low surface roughness value.

The method of preparing the thermoplastic resin composition has all the technical features of the above thermoplastic resin composition, and thus a repetitive description thereof will be omitted.

The step of preparing pellets using an extrusion compounder is preferably carried out at 220 ℃ to 280 ℃, more preferably at 240 ℃ to 280 ℃. In this case, the temperature is the temperature of the cylinder.

An extrusion kneader generally used in the art to which the present invention pertains may be used without particular limitation, and a twin-screw extrusion kneader is preferably used.

Molded article

The molded article of the present invention comprises the thermoplastic resin composition of the present invention. In this case, the molded article of the present invention may have mechanical properties and processability equal to or better than those of conventional molded articles, may have excellent weather resistance and low gloss, may exhibit uniform surface gloss, and may exhibit good aesthetic properties and soft feeling due to its low surface roughness value.

For example, the molded article may be an extrusion molded article or an injection molded article, preferably an architectural exterior material, more preferably a side door or window, or a sliding door or window.

Preferably, the molded article is prepared by extruding or injecting the thermoplastic resin composition of the present invention at a molding temperature of 190 ℃ to 250 ℃. Within this range, an excellent matte effect can be achieved.

In describing the thermoplastic resin composition of the present invention, the method for preparing the same, and the molded article comprising the same, other conditions or equipment not specifically described may be appropriately selected within the scope generally practiced in the art without specific limitations.

Hereinafter, the present invention will be described in more detail with reference to the following preferred examples. However, these examples are provided for illustrative purposes only, and should not be construed as limiting the scope and spirit of the present invention. In addition, it will be apparent to those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention, and such changes and modifications are also within the scope of the appended claims.

[ examples ]

The substances used in examples 1 to 10 and comparative examples 1 to 3 are as follows.

A-1) first graft copolymer according to emulsion polymerization (50% by weight of a butyl acrylate polymer having an average particle diameter of 100nm, shell: 36% by weight of styrene, 14% by weight of acrylonitrile)

A-2) second graft copolymer according to emulsion polymerization (50% by weight of a butyl acrylate polymer having an average particle diameter of 400nm, shell: 38% by weight of styrene, 12% by weight of acrylonitrile)

B-1) SAN resin (92RF) polymerized according to the bulk

B-2) Heat-resistant SAN resin (200UH) according to bulk polymerization

C-1) SAMMA resin according to bulk polymerization (XT500)

C-2) SAMMA resin polymerized according to the bulk (XT510)

C-3) PMMA resin (IH830)

C-4) PMMA resin (BA611)

D)PA 6.6

Examples 1 to 10 and comparative examples 1 to 3

As shown in table 1 below, components were prepared according to contents and kneaded and extruded at 280 ℃ using a twin-screw extruder to prepare pellets. In addition, 0.15T sheets were prepared using the pellets prepared at a molding temperature of 220 ℃. Then, the gloss and surface roughness values of the film were measured. In addition, the prepared pellets were injected at a molding temperature of 220 ℃ to prepare test specimens for measuring physical properties. Then, the tensile strength and impact strength of the test piece were measured.

[ test examples ]

The physical properties of the pellets, sheets and test specimens prepared in examples 1 to 10 and comparative examples 1 to 3 were measured according to the following methods, and the results are shown in table 1 below.

Melt Index (MI): the melt index of the prepared pellets was measured at 220 ℃/10kg according to ASTM D1238.

Tensile Strength (kg/cm)²): tensile strength was measured according to ASTM 638.

Izod impact strength (kg.cm/cm): izod impact strength was measured according to ASTM 256.

Film gloss: the film gloss was measured at 60 ℃ using a gloss meter (product name: VG 7000).

Surface roughness value: surface roughness values of 5 points were measured in a WSI Envelope mode and a scanning range of + -30 μm using an optical profiler System (NV-2700, Nano System Co., Ltd.) using an objective lens (. times.10) and an eyepiece lens (. times.1) (F.O.V.: 628. mu. m.times.471 μm), and the average thereof was calculated. As the surface roughness value decreases, the soft touch and gloss increase.

Weather resistance: the weather resistance was measured for 2,000 hours according to SAE J1960, and the weather resistance (Δ E) value was obtained by the following equation 1. As the weather resistance (Δ E) value decreases, the weather resistance increases.

[ equation 1]

[ Table 1]

As shown in table 1, it can be confirmed that the thermoplastic resin compositions according to the present invention (example 1 to example 10) have mechanical properties, such as melt index, tensile strength and impact strength, equal to or better than those of the thermoplastic resin compositions of comparative example 1 and comparative example 2 not containing a polymethacrylate resin; has excellent weather resistance; exhibits good aesthetics and soft feel due to its low surface roughness value; and has uniform surface gloss and low surface gloss. Specifically, as shown in table 1, examples 1 to 3 and examples 7 to 9, which include 40 to 60 wt%, more specifically 45 to 55 wt% of the polymethacrylate resin, exhibited surface roughness values of 3.0 or less, specifically 2.0 to 3.0, and weather resistance (Δ E) values of 3.1 or less, specifically 1.3 to 3.3. Based on these results, it can be seen that the resins of examples 1 to 3 and examples 7 to 9 have high quality and excellent aesthetic properties as compared with comparative examples 1 and 2.

In addition, comparative example 3, which does not contain polyamide, exhibits a gloss of 67, which is 6 to 14 times as high as that of examples 1 to 9. The results show that comparative example 3 does not satisfy the object of the present invention to prepare an aesthetically pleasing resin having matte properties and high quality.

Claims

1. A thermoplastic resin composition comprising:

100 parts by weight of a base resin consisting of 10 to 30% by weight of an acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (a-1) containing an acrylate rubber having an average particle diameter of 0.05 to 0.15 μm, 20 to 40% by weight of an acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (a-2) containing an acrylate rubber having an average particle diameter of 0.3 to 0.5 μm, 0 to 35% by weight of an aromatic vinyl polymer (B), and 10 to 60% by weight of a polymethacrylate (C); and

0.5 to 10 parts by weight of a polyamide (D).

2. The thermoplastic resin composition according to claim 1, wherein said thermoplastic resin composition has matte properties based on the result that the film gloss measured at 60 ° using a gloss meter (product name: VG7000) of said thermoplastic resin composition is 14 or less.

3. The thermoplastic resin composition of claim 1, wherein the thermoplastic resin composition has an average surface roughness value of 5 points of 4 or less as measured using an optical profilometer system.

4. The thermoplastic resin composition of claim 1, wherein said thermoplastic resin composition has a weatherability (Δ E) value of 4.0 or less as measured according to SAE J1960.

5. The thermoplastic resin composition of claim 1, wherein the graft copolymer (a-1) comprises 40 to 60% by weight of the acrylate rubber, 25 to 45% by weight of the aromatic vinyl compound, and 10 to 20% by weight of the vinyl cyanide compound.

6. The thermoplastic resin composition of claim 1, wherein the graft copolymer (a-2) comprises 40 to 60% by weight of the acrylate rubber, 25 to 45% by weight of the aromatic vinyl compound, and 10 to 20% by weight of the vinyl cyanide compound.

7. The thermoplastic resin composition according to claim 1, wherein said graft copolymer (A-1) is contained in a smaller amount than said graft copolymer (A-2).

8. The thermoplastic resin composition of claim 1, wherein the total weight of said graft copolymer (a-1) and said graft copolymer (a-2) is 40 to 60% by weight based on the weight of said base resin.

9. The thermoplastic resin composition according to claim 1, wherein the aromatic vinyl polymer (B) is contained in an amount of 10 to 35% by weight.

10. The thermoplastic resin composition of claim 1, wherein the aromatic vinyl polymer (B) is present in an amount of less than 10 wt.% or is absent.

11. The thermoplastic resin composition according to claim 1, wherein said aromatic vinyl polymer (B) is an aromatic vinyl compound-vinyl cyan compound copolymer.

12. The thermoplastic resin composition according to claim 1, wherein the polymethacrylate resin (C) contains 55 wt% or more of a methacrylate monomer.

13. The thermoplastic resin composition according to claim 12, wherein the polymethacrylate resin (C) comprises one or more selected from the group consisting of a polymethylmethacrylate resin and a methylmethacrylate-styrene-acrylonitrile copolymer.

14. The thermoplastic resin composition of claim 13, wherein said methyl methacrylate-styrene-acrylonitrile copolymer comprises 65 to 85 wt% of methyl methacrylate, 5 to 30 wt% of styrene, and 5 to 10 wt% of acrylonitrile.

15. The thermoplastic resin composition according to claim 1, wherein said polyamide (D) is polyamide 6.6.

16. A molded article comprising the thermoplastic resin composition of any one of claims 1 to 15.